Naphthalenetetracarboxylic acid derivatives and their use as semiconductors

ABSTRACT

The present invention relates to naphthalenetetracarboxylic acid derivates, to a process for their preparation and to their use, especially as an n-type semiconductor.

This application is a 371 of PCT/EP2006/070143, filed Dec. 22, 2006.

The present invention relates to naphthalenetetracarboxylic acidderivates, to a process for their preparation and to their use,especially as n-type semiconductors.

In many fields of the electronics industry, organic semiconductors basedon low molecular weight or polymeric materials are increasingly alsobeing used in addition to the classical inorganic semiconductors. Theformer in many cases have advantages over the classical inorganicsemiconductors, for example, better substrate compatibility, betterprocessibility of the semiconductor components based on them, greaterflexibility, reduced costs and the possibility of adjusting theirfrontier orbital energies to the particular field of use with themethods of molecular design. A main field of use in the electronicsindustry is that of so-called field-effect transistors (FETs). A greatpotential for development, for example, in storage elements andintegrated optoelectronic devices is ascribed to organic field-effecttransistors (OFETs). There is therefore a great need for organiccompounds which are suitable as organic semiconductors, in particularn-type semiconductors, and especially for use in organic field-effecttransistors.

DE-A-32 35 526 relates to perylene-3,4,9,10-tetracarboximides, which aresubstituted on the perylene skeleton by alkoxy or alkylthio groups, andalso by fluorine, chlorine or bromine, to a process for theirpreparation and to their use in light-collecting plastics.

DE-A-195 47 209 relates to 1,7-diaryloxy- or 1,7-diarylthio-substitutedperylene-3,4,9,10-tetracarboxylic acids and to their dianhydrides anddiimides. For their preparation,1,7-dibromoperylene-3,4,9,10-tetracarboximides are used asintermediates. The preparation of this dibromo compound succeedsstarting from perylene-3,4,9,10-tetracarboxylic dianhydride bybromination in the presence of iodine and sulfuric acid.

In J. Am. Chem. Soc. 2004, 126, pp. 8284-8294, M. J. Ahrens et al.describe self-assembling, supermolecular, light-collecting arrays ofcovalent, multichromophoric perylene-3,4,9,10-bis(dicarboximide) repeatunits.

In Chem. Mater. 2003, 15, pp. 2684-2686, M. J. Ahrens, M. J. Fuller andM. R. Wasielewski describe cyano-substituted perylene-3,4-dicarboximidesand perylene-3,4,9,10-bis(dicarboximide) and their use as chromophoricoxidizing agents, for example for use in photonics and electronics.

In Angew. Chem. 2004, 116, pp. 6523-6526, B. A. Jones et al. describethe use of dicyanoperylene-3,4,9,10-bis(dicarboximides) asn-semiconductors.

US 2005/0176970 A1 describes n-semiconductors based on substitutedperylene-3,4-dicarboximides and perylene-3,4,9,10-bis(dicarboximides).This document quite generally, and without any evidence by way of apreparation example, also describes substitutednaphthalene-1,8-dicarboximides andnaphthalene-1,4;5,8-bis(dicarboximides) and their use asn-semiconductors. Intermediates mentioned for the preparation of theperylenes are 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydrideand the corresponding 1,7-dibromoperylene-3,4,9,10-bis(dicarboximide),and with regard to their preparation, reference is made to thepossibility of directly brominating the corresponding startinghydrocarbon compound. Unlike the perylenes, the corresponding2,6-dibrominated naphthalenes are, however, not obtainable by directbromination, for example in the presence of iodine and sulfuric acid.

In his thesis, C. H. Thalacker, University of Ulm, 2001, describessupramolecular arrangements of naphthalene- and perylenebisimide dyesbased on hydrogen bonds and π-π interactions. On pages 136 and 147 to148 of this document, the synthesis of2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride isdescribed, but an imidation of only one of the two anhydride groups didnot succeed.

DE 101 48 172 A1 describes naphthalene-1,8;4,5-tetracarboxylic bisimidesof the general formula

in which

-   R¹ and R² are each independently hydrogen, substituted or    unsubstituted alkyl or substituted or unsubstituted aryl, and-   X and Y are each independently hydrogen, halogen, amino or a radical    of the formula —NHR³ or —OR³, where R³ is —CH₂R⁴, —CHR⁴R⁵ or    —CR⁴R⁵R⁶, where R⁴, R⁵, R⁶ are each independently hydrogen,    substituted or unsubstituted alkyl, aryl, alkoxy, alkylthio, aryloxy    or arylthio, where at least one of the two substituents X and Y is    not hydrogen or halogen.

One possible starting material mentioned for the preparation of thesecompounds is 2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydrideand, without specific details, reference is made to known methods forpreparing the corresponding2,5-dibromonaphthalene-1,8;4,5-tetracarboximides. In contradiction tothis and in agreement with the abovementioned thesis by Thalacker,working example 4, however, describes the imidation of2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic dianhydride with2-ethylhexylamine, which simultaneously substitutes the bromine atomsbonded to the aromatic base structure by 2-ethylhexylamino groups. Aworkable synthesis for the preparation of2,6-dibromonaphthalene-1,8;4,5-tetracarboximides is thus disclosedneither in DE 101 48 172 A1 nor in the thesis by Thalacker.

It is an object of the present invention to provide novel compoundswhich are suitable as n-semiconductors, for example for use in organicfield-effect transistors.

This object is achieved by a compound of the general formula I

whereat least one of the R¹, R², R³ and R⁴ radicals is a substituent which isselected from Br, F and CN,Y¹ is O or NR^(a), where R^(a) is hydrogen or an organyl radical,Y² is O or NR^(b), where R^(b) is hydrogen or an organyl radical,Z¹ and Z² are each independently O or NR^(c), where R^(c) is an organylradical,Z³ and Z⁴ are each independently O or NR^(d), where R^(d) is an organylradical,where, in the case that Y¹ is NR^(a) and at least one of the Z¹ and Z²radicals is NR^(c), R^(a) with one R^(c) radical may also together be abridging group having 2 to 5 atoms between the flanking bonds, andwhere, in the case that Y² is NR^(b) and at least one of the Z³ and Z⁴radicals is NR^(d), R^(b) with one R^(d) radical may also together be abridging group having 2 to 5 atoms between the flanking bonds.

In the context of the present invention, the term “alkyl” comprisesstraight-chain or branched alkyl. It is preferably straight-chain orbranched C₁-C₃₀-alkyl, in particular C₁-C₂₀-alkyl and most preferablyC₁-C₁₂-alkyl. Examples of alkyl groups are in particular methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl,1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl,1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl,1,1,3,3-tetramethylbutyl, nonyl, decyl, n-undecyl, n-dodecyl,n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl andn-eicosyl.

The term alkyl also comprises alkyl radicals, whose carbon chains may beinterrupted by one or more nonadjacent groups which are selected from—O—, —S—, —NR^(e)—, —CO— and/or —SO₂—, i.e. the termini of the alkylgroup are formed by carbon atoms. R^(e) is preferably hydrogen, alkyl,cycloalkyl, heterocycloalkyl, aryl or hetaryl.

The above remarks on alkyl also apply to the alkyl moieties in alkoxy,alkylamino, alkylthio, alkylsulfinyl and alkylsulfonyl.

In the context of the present invention, the term “alkenyl” comprisesstraight-chain and branched alkenyl groups which, depending on the chainlength, may bear one or more double bonds. Preference is given toC₂-C₂₀-alkenyl, particular preference to C₂-C₁₀-alkenyl groups. The term“alkenyl” also comprises substituted alkenyl groups, which may bear, forexample, 1, 2, 3, 4 or 5 substituents. Suitable substituents are, forexample, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, cyano,halogen, amino, mono- or di-(C₁-C₂₀-alkyl)amino.

Alkenyl is then, for example, ethenyl, 1-propenyl, 2-propenyl,1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-3-butenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl,3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl,1-ethyl-2-methyl-2-propenyl, 1,3-butadienyl, 1-methyl-1,3-butadienyl,2-methyl-1,3-butadienyl, penta-1,3-dien-1-yl, hexa-1,4-dien-1-yl,hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, hexa-1,5-dien-1-yl,hexa-1,5-dien-3-yl, hexa-1,5-dien-4-yl, hepta-1,4-dien-1-yl,hepta-1,4-dien-3-yl, hepta-1,4-dien-6-yl, hepta-1,4-dien-7-yl,hepta-1,5-dien-1-yl, hepta-1,5-dien-3-yl, hepta-1,5-dien-4-yl,hepta-1,5-dien-7-yl, hepta-1,6-dien-1-yl, hepta-1,6-dien-3-yl,hepta-1,6-dien-4-yl, hepta-1,6-dien-5-yl, hepta-1,6-dien-2-yl,octa-1,4-dien-1-yl, octa-1,4-dien-2-yl, octa-1,4-dien-3-yl,octa-1,4-dien-6-yl, octa-1,4-dien-7-yl, octa-1,5-dien-1-yl,octa-1,5-dien-3-yl, octa-1,5-dien-4-yl, octa-1,5-dien-7-yl,octa-1,6-dien-1-yl, octa-1,6-dien-3-yl, octa-1,6-dien-4-yl,octa-1,6-dien-5-yl, octa-1,6-dien-2-yl, deca-1,4-dienyl,deca-1,5-dienyl, deca-1,6-dienyl, deca-1,7-dienyl, deca-1,8-dienyl,deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl andthe like. The remarks on alkenyl also apply to the alkenyl groups inalkenyloxy, alkenylthio, etc.

The term “alkynyl” comprises unsubstituted or substituted alkynylgroups, which have one or more nonadjacent triple bonds such as ethynyl,1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl,1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl,2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl,3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl,1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl andthe like. The remarks on alkynyl also apply to the alkynyl groups inalkynyloxy, alkynylthio, etc.

In the context of the present invention, the term “cycloalkyl” comprisesboth unsubstituted and substituted cycloalkyl groups, preferablyC₃-C₈-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl or cyclooctyl, in particular C₅-C₈-cycloalkyl.In the case of substitution, the cycloalkyl groups may bear one or more,for example one, two, three, four or five, C₁-C₆-alkyl groups.

C₅-C₈-cycloalkyl which is unsubstituted or may bear one or moreC₁-C₆-alkyl groups is, for example, cyclopentyl, 2- and3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-,3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-,3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4-and 5-propylcyclooctyl.

The term cycloalkenyl comprises preferably monocyclic, monounsaturatedhydrocarbon groups having from 3 to 8, preferably from 5 to 6, carbonring members, such as cyclopenten-1-yl, cyclopenten-3-yl,cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like.

The term bicycloalkyl comprises preferably bicyclic hydrocarbon radicalshaving from 5 to 10 carbon atoms, such as bicyclo[2.2.1]hept-1-yl,bicyclo[2.2.1]hept-2-yl, bicyclo[2.2.1]hept-7-yl,bicyclo[2.2.2]oct-1-yl, bicyclo[2.2.2]oct-2-yl, bicyclo[3.3.0]octyl,bicyclo[4.4.0]decyl and the like.

In the context of the present invention, the term “aryl” comprises mono-or polycyclic aromatic hydrocarbon radicals which may be unsubstitutedor substituted. The term “aryl” preferably represents phenyl, tolyl,xylyl, mesityl, duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenylor naphthyl, more preferably phenyl or naphthyl, where these arylgroups, in the case of substitution, may generally bear 1, 2, 3, 4 or 5,preferably 1, 2 or 3 substituents which are selected from C₁-C₁₈-alkyl,C₁-C₆-alkoxy, cyano, CONR^(f)R^(g), CO₂R^(f), arylazo and heteroarylazo,where arylazo and heteroarylazo are in turn unsubstituted or bear one ormore radicals which are each independently selected from C₁-C₁₈-alkyl,C₁-C₆-alkoxy and cyano. R^(f) and R^(g) are each independently hydrogen,alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Aryl, which is unsubstituted or bears one or more radicals which areeach independently selected from C₁-C₁₈-alkyl, C₁-C₆-alkoxy and cyanois, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl,2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl,2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5-and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl,2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl,2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-,3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3-and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-cyanophenyl.

In the context of the present invention, the term “heterocycloalkyl”comprises nonaromatic, unsaturated or fully saturated, cycloaliphaticgroups having generally from 5 to 8 ring atoms, preferably 5 or 6 ringatoms, in which 1, 2 or 3 of the ring carbon atoms are replaced byheteroatoms selected from oxygen, nitrogen, sulfur and an —NR^(e)— groupand which is unsubstituted or substituted by one or more, for example,1, 2, 3, 4, 5 or 6 C₁-C₆-alkyl groups. Examples of suchheterocycloaliphatic groups include pyrrolidinyl, piperidinyl,2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl,oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl,isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothien-2-yl,tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl,1,2-oxazolin-5-yl, 1,3-oxazolin-2-yl and dioxanyl.

In the context of the present invention, the term “heteroaryl” comprisesunsubstituted or substituted, heteroaromatic, mono- or polycyclicgroups, preferably the pyridyl, quinolinyl, acridinyl, pyridazinyl,pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl,purinyl, indazolyl, benzotriazolyl, 1,2,3-triazolyl, 1,3,4-triazolyl andcarbazolyl groups, where these heterocycloaromatic groups, in the caseof substitution, may generally bear 1, 2 or 3 substituents. Thesubstituents are selected from C₁-C₆-alkyl, C₁-C₆-alkoxy, hydroxyl,carboxyl and cyano.

5- to 7-membered heterocycloalkyl or heteroaryl radicals, which arebonded via a nitrogen atom and, if appropriate, comprise furtherheteroatoms are, for example, pyrrolyl, pyrazolyl, imidazolyl,triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl,imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl,triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl,isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl.

Halogen is fluorine, chlorine, bromine or iodine.

Specific examples of the radicals mentioned in the following formulaeand their substituents are:

methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl,1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl,isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (theabove terms isooctyl, isononyl, isodecyl and isotridecyl are trivialterms and stem from the alcohols obtained by the oxo process);2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxamidecyl and3,6,9,12-tetraoxatetradecyl;2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 2- and4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl,3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiamidecyland 3,6,9,12-tetrathiatetradecyl;2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazamidecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazamidecyl;(1-ethylethylidene)aminoethylene, (1-ethylethylidene)aminopropylene,(1-ethylethylidene)aminobutylene, (1-ethylethylidene)aminodecylene and(1-ethylethylidene)aminododecylene;propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;2-methylsulfoxidoethyl, 2-ethylsulfoxidoethyl, 2-propylsulfoxidoethyl,2-isopropylsulfoxidoethyl, 2-butylsulfoxidoethyl, 2- and3-methylsulfoxidopropyl, 2- and 3-ethylsulfoxidopropyl, 2- and3-propylsulfoxidopropyl, 2- and 3-butylsulfoxidopropyl, 2- and4-methylsulfoxidobutyl, 2- and 4-ethylsulfoxidobutyl, 2- and4-propylsulfoxidobutyl and 4-butylsulfoxidobutyl;2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl,2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl,12-carboxydodecyl and 14-carboxytetradecyl;sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl,6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and14-sulfotetradecyl;2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 3- and4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxaoctyl;2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl,2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and4,7-dimethyl-7-cyanoheptyl;2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl,2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl;2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl;methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy,tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy;methylthio, ethylthio, propylthio, isopropylthio, butylthio,isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio,neopentylthio, tert-pentylthio and hexylthio;ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and4-pentynyl, 1-, 2-, 3-, 4- and 5-hexynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecynyland 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-,16- and 17-octadecynyl;ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecenyland 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-,16- and 17-octadecenyl;methylamino, ethylamino, propylamino, isopropylamino, butylamino,isobutylamino, pentylamino, hexylamino, dimethylamino, methylethylamino,diethylamino, dipropylamino, diisopropylamino, dibutylamino,diisobutylamino, dipentylamino, dihexylamino, dicyclopentylamino,dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;formylamino, acetylamino, propionylamino and benzoylamino;carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl,heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl,decylaminocarbonyl and phenylaminocarbonyl;aminosulfonyl, N,N-dimethylaminosulfonyl, N,N-diethylaminosulfonyl,N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl,N-dodecylaminosulfonyl, (N,N-dimethylamino)ethylaminosulfonyl,N,N-(propoxyethyl)dodecylaminosulfonyl, N,N-diphenylaminosulfonyl,N,N-(4-tert-butylphenyl)octadecylaminosulfonyl andN,N-bis(4-chlorophenyl)aminosulfonyl;methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl,phenoxycarbonyl, (4-tert-butylphenoxy)carbonyl and(4-chlorophenoxy)carbonyl;methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl,butoxysulfonyl, isobutoxysulfonyl, tert-butoxysulfonyl, hexoxysulfonyl,dodecyloxysulfonyl, octadecyloxysulfonyl, phenoxysulfonyl, 1- and2-naphthyloxysulfonyl, (4-tert-butylphenoxy)sulfonyl and(4-chlorophenoxy)sulfonyl;diphenylphosphino, di(o-tolyl)phosphino and diphenylphosphinoxido;fluorine, chlorine, bromine and iodine;phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3-and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-,3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl,2-, 3-, 4- and 5-ethylcyclooctyl and 3-, 4- and 5-propylcyclooctyl; 3-and 4-hydroxycyclohexyl, 3- and 4-nitrocyclohexyl and 3- and4-chlorocyclohexyl;1-, 2- and 3-cyclopentenyl, 1-, 2-, 3- and 4-cyclohexenyl, 1-, 2- and3-cycloheptenyl and 1-, 2-, 3- and 4-cyclooctenyl;2-dioxanyl, 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl,1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3-and 4-piperidyl;phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5-imidazolyl, 2-, 4- and5-thiazolyl, 3-(1,2,4-triazyl), 2-(1,3,5-triazyl), 6-quinaldyl, 3-, 5-,6- and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl,5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;1-, 2-, 3-, 4-, 5-, 6- and 7-indolyl, 1-, 2-, 3-, 4-, 5-, 6- and7-isoindolyl, 5-(4-methylisoindolyl), 5-(4-phenylisoindolyl), 1-, 2-,4-, 6-, 7- and 8-(1,2,3,4-tetrahydroisoquinolinyl),3-(5-phenyl)-(1,2,3,4-tetrahydroisoquinolinyl),5-(3-dodecyl)-(1,2,3,4-tetrahydroisoquinolinyl), 1-, 2-, 3-, 4-, 5-, 6-,7- and 8-(1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, 4-, 5-, 6-, 7- and8-chromanyl, 2-, 4- and 7-quinolinyl, 2-(4-phenylquinolinyl) and2-(5-ethylquinolinyl);2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl,2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and4-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and2,4,6-tri-sec-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl,2,4-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl;3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3-and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl;3- and 4-N-phenylaminophenyl, 3- and 4-N-(o-tolyl)aminophenyl, 3- and4-N-(m-tolyl)aminophenyl and 3- and 4-(p-tolyl)aminophenyl; 3- and4-(2-pyridyl)aminophenyl, 3- and 4-(3-pyridyl)aminophenyl, 3- and4-(4-pyridyl)aminophenyl, 3- and 4-(2-pyrimidyl)aminophenyl and4-(4-pyrimidyl)aminophenyl;4-phenylazophenyl, 4-(1-naphthylazo)phenyl, 4-(2-naphthylazo)phenyl,4-(4-naphthylazo)phenyl, 4-(2-pyridylazo)phenyl, 4-(3-pyridylazo)phenyl,4-(4-pyridylazo)phenyl, 4-(2-pyrimidylazo)phenyl,4-(4-pyrimidylazo)phenyl and 4-(5-pyrimidylazo)phenyl;phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and2-, 4- and 5-pyrimidylthio.

Preferred fluorinated radicals are the following:

2,2,2-trifluoroethyl, 2,2,3,3,4,4,4-heptafluorobutyl,2,2,3,3,3-pentafluoropropyl, 1H, 1H-pentadecafluorooctyl,2,2-difluoroethyl, 2,2,2-trifluoro-1-phenylethylamine,1-benzyl-2,2,2-trifluoroethyl, 1H, 1H-perfluoroheptyl, 1H,1H-perfluorononyl, 2-bromo-2,2-difluoroethyl,2,2,2-trifluoro-1,1-dimethylethyl, 2,2,2-trifluoro-1-(methyl)ethyl,1,1,1-trifluoroisopropyl, 2,2,2-trifluoro-1-pyridin-2-ylethyl,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-nonadecafluorodecyl,3,5,7,8-tetrabromo-2,2,3,4,4,5,6,6,7,8,8-undecafluorooctyl,2,2,3,3,4,4,5,5-octafluoropentyl, 1H,1H-perfluoropentyl,2,2-difluoropropyl, 2,2,2-trifluoro-1-(4-methoxyphenyl)ethylamine,2,2,2-trifluoro-1-phenylethylamine, 2,2-difluoro-1-phenylethylamine,1-(4-bromophenyl)-2,2,2-trifluoroethyl, 3-bromo-3,3-difluoropropyl,3,3,3-trifluoropropylamine, 3,3,3-trifluoro-n-propyl,1H,1H,2H,2H-perfluorodecyl, 3-(perfluorooctyl)propyl, 4,4-difluorobutyl,4,4,4-trifluorobutyl, 5,5,6,6,6-pentafluorohexyl, 2-fluorophenyl,pentafluorophenyl, 2,3,5,6-tetrafluorophenyl,4-cyano-(2,3,5,6)-tetrafluorophenyl,4-carboxy-2,3,5,6-tetrafluorophenyl, 2,4-difluorophenyl,2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 2,5-difluorophenyl,2-fluoro-5-nitrophenyl, 2-fluoro-5-trifluoromethylphenyl,2-fluoro-5-methylphenyl, 2,6-difluorophenyl,4-carboxamido-2,3,5,6-tetrafluorophenyl, 2-bromo-4,6-difluorophenyl,4-bromo-2-fluorophenyl, 2,3-difluorophenyl, 4-chloro-2-fluorophenyl,2,3,4-trifluorophenyl, 2-fluoro-4-iodophenyl,4-bromo-2,3,5,6-tetrafluorophenyl, 2,3,6-trifluorophenyl,2-bromo-3,4,6-trifluorophenyl, 2-bromo-4,5,6-trifluorophenyl,4-bromo-2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl,2,4-difluoro-6-nitrophenyl, 2-fluoro-4-nitrophenyl,2-chloro-6-fluorophenyl, 2-fluoro-4-methylphenyl,3-chloro-2,4-difluorophenyl, 2,4-dibromo-6-fluorophenyl,3,5-dichloro-2,4-difluorophenyl, 4-cyano-1-fluorophenyl,1-chloro-4-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl,2-trifluoromethyl-6-fluorophenyl, 2,3,4,6-tetrafluorophenyl,3-chloro-2-fluorophenyl, 5-chloro-2-fluorophenyl,2-bromo-4-chloro-6-fluorophenyl, 2,3-dicyano-4,5,6-trifluorophenyl,2,4,5-trifluoro-3-carboxyphenyl, 2,3,4-trifluoro-6-carboxyphenyl,2,3,5-trifluorophenyl, 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl,1-fluoro-5-carboxyphenyl, 2-chloro-4,6-difluorophenyl,6-bromo-3-chloro-2,4-difluorophenyl, 2,3,4-trifluoro-6-nitrophenyl,2,5-difluoro-4-cyanophenyl, 2,5-difluoro-4-trifluoromethylphenyl,2,3-difluoro-6-nitrophenyl, 4-trifluoromethyl-2,3-difluorophenyl,2-bromo-4,6-difluorophenyl, 4-bromo-2-fluorophenyl,2-nitrotetrafluorophenyl, 2,2′,3,3′,4′,5,5′,6,6′-nonabiphenyl,2-nitro-3,5,6-trifluorophenyl, 2-bromo-6-fluorophenyl,4-chloro-2-fluoro-6-iodophenyl, 2-fluoro-6-carboxyphenyl,2,4-difluoro-3-trifluorophenyl, 2-fluoro-4-trifluorophenyl,2-fluoro-4-carboxyphenyl, 4-bromo-2,5-difluorophenyl,2,5-dibromo-3,4,6-trifluorophenyl, 2-fluoro-5-methylsulfonylphenyl,5-bromo-2-fluorophenyl, 2-fluoro-4-hydroxymethylphenyl,3-fluoro-4-bromomethylphenyl, 2-nitro-4-trifluoromethylphenyl,4-trifluoromethylphenyl, 2-bromo-4-trifluoromethylphenyl,2-bromo-6-chloro-4-(trifluoromethyl)phenyl,2-chloro-4-trifluoromethylphenyl, 3-nitro-4-(trifluoromethyl)phenyl,2,6-dichloro-4-(trifluoromethyl)phenyl, 4-trifluorophenyl,2,6-dibromo-4-(trifluoromethyl)phenyl,4-trifluoromethyl-2,3,5,6-tetrafluorophenyl,3-fluoro-4-trifluoromethylphenyl, 2,5-difluoro-4-trifluoromethylphenyl,3,5-difluoro-4-trifluoromethylphenyl,2,3-difluoro-4-trifluoromethylphenyl, 2,4-bis(trifluoromethyl)phenyl,3-chloro-4-trifluoromethylphenyl, 2-bromo-4,5-di(trifluoromethyl)phenyl,5-chloro-2-nitro-4-(trifluoromethyl)phenyl,2,4,6-tris(trifluoromethyl)phenyl, 3,4-bis(trifluoromethyl)phenyl,2-fluoro-3-trifluoromethylphenyl, 2-iodo-4-trifluoromethylphenyl,2-nitro-4,5-bis(trifluoromethyl)phenyl,2-methyl-4-(trifluoromethyl)phenyl,3,5-dichloro-4-(trifluoromethyl)phenyl,2,3,6-trichloro-4-(trifluoromethyl)phenyl, 4-(trifluoromethyl)benzyl,2-fluoro-4-(trifluoromethyl)benzyl, 3-fluoro-4-(trifluoromethyl)benzyl,3-chloro-4-(trifluoromethyl)benzyl, 4-fluorophenethyl,3-(trifluoromethyl)phenethyl, 2-chloro-6-fluorophenethyl,2,6-dichlorophenethyl, 3-fluorophenethyl, 2-fluorophenethyl,(2-trifluoromethyl)phenethyl, 4-trifluoromethylphenethyl,2,3-difluorophenethyl, 3,4-difluorophenethyl, 2,4-difluorophenethyl,2,5-difluorophenethyl, 3,5-difluorophenethyl, 2,6-difluorophenethyl,4-(4-fluorophenyl)phenethyl, 3,5-di(trifluoromethyl)phenethyl,pentafluorophenethyl, 2,4-di(trifluoromethyl)phenethyl,2-nitro-4-(trifluoromethyl)phenethyl,(2-fluoro-3-trifluoromethyl)phenethyl,(2-fluoro-5-trifluoromethyl)phenethyl,(3-fluoro-5-trifluoromethyl)phenethyl,(4-fluoro-2-trifluoromethyl)phenethyl,(4-fluoro-3-trifluoromethyl)phenethyl,(2-fluoro-6-trifluoromethyl)phenethyl, (2,3,6-trifluoro)phenethyl,(2,4,5-trifluoro)phenethyl, (2,4,6-trifluoro)phenethyl,(2,3,4-trifluoro)phenethyl, (3,4,5-trifluoro)phenethyl,(2,3,5-trifluoro)phenethyl, (2-chloro-5-fluoro)phenethyl,(3-fluoro-4-trifluoromethyl)phenethyl,(2-chloro-5-trifluoromethyl)phenethyl,(2-fluoro-3-chloro-5-trifluoromethyl)phenethyl,(2-fluoro-3-chloro)phenethyl, (4-fluoro-3-chloro)phenethyl,(2-fluoro-4-chloro)phenethyl, (2,3-difluoro-4-methyl)phenethyl,2,6-difluoro-3-chlorophenethyl, (2,6-difluoro-3-methyl)phenethyl,(2-trifluoromethyl-5-chloro)phenethyl,(6-chloro-2-fluoro-5-methyl)phenethyl, (2,4-dichloro-5-fluoro)phenethyl,5-chloro-2-fluorophenethyl, (2,5-difluoro-6-chloro)phenethyl,(2,3,4,5-tetrafluoro)phenethyl, (2-fluoro-4-trifluoromethyl)phenethyl,2,3-(difluoro-4-trifluoromethyl)phenethyl,(2,5-di(trifluoromethyl))phenethyl, 2-fluoro-3,5-dibromophenethyl,(3-fluor-4-nitro)phenethyl, (2-bromo-4-trifluoromethyl)phenethyl,2-(bromo-5-fluoro)phenethyl, (2,6-difluoro-4-bromo)phenethyl,(2,6-difluoro-4-chloro)phenethyl, (3-chloro-5-fluoro)phenethyl,(2-bromo-5-trifluoromethyl)phenethyl and the like.

In a specific embodiment, the compounds of the formula I are not thosein which Z¹, Z², Z³, Z⁴, Y¹ and Y² are O and the R¹ to R⁴ radicals areselected from hydrogen and bromine.

More specifically, the compounds of the formula I are not those in whichZ¹, Z², Z³, Z⁴, Y¹ and Y² are O and R¹ and R⁴ or R² and R³ are bothbromine. In other words, in a specific embodiment,2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic dianhydrides are excludedfrom the compounds of the formula I.

Preference is given to compounds of the formula I, where R¹, R², R³ andR⁴ are each bromine or are each fluorine or are each cyano.

Preference is further given to compounds of the formula I, where threeof the R¹, R², R³ and R⁴ radicals are each bromine or are each fluorineor are each cyano, and the remaining radical is hydrogen.

Preference is further given to compounds of the formula I, where R¹ andR² are each independently selected from fluorine and cyano, and R³ andR⁴ are each hydrogen. In a preferred embodiment, R¹ and R² are then eachfluorine or are each cyano.

Preference is further given to compounds where R¹ and R³ are eachindependently selected from fluorine and cyano, and R² and R⁴ are eachhydrogen. In a preferred embodiment, R¹ and R³ are then each fluorine orare each cyano.

Preference is further given to compounds where R¹ and R⁴ are eachindependently selected from fluorine and cyano, and R² and R³ are eachhydrogen. In a preferred embodiment, R¹ and R⁴ are then each fluorine orare each cyano.

Preference is further given to compounds where R¹ and R² are eachbromine and R³ and R⁴ are each hydrogen.

Preference is further given to compounds where one of the R¹, R², R³ andR⁴ radicals is bromine or is fluorine or is cyano, and the remainingradicals are each hydrogen.

Particular preference is given to compounds of the formula I.a

in whichR¹, R², R³ and R⁴ are each as defined above.

With regard to the definitions of the substituents R^(a) and R^(b) inthe compounds of the formula I, reference is made to the remarks made atthe outset.

R^(a) and R^(b) are preferably each independently hydrogen orunsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl,cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl orheteroaryl.

More preferably, at least one of the R^(a) and R^(b) radicals is aradical with electron-withdrawn substituents.

In a specific embodiment, at least one of the R^(a) and R^(b) radicalsis a radical mono- or polysubstituted by fluorine. More preferably, bothR^(a) and R^(b) are a radical mono- or polysubstituted by fluorine. Withregard to suitable fluorinated radicals, reference is likewise made tothe remarks made at the outset.

In a further specific embodiment, the R^(a) and R^(b) radicals areidentical.

Particular preference is further given to compounds of the generalformula I.b

in whichR¹, R², R³ and R⁴ are each as defined above andR^(a) and R^(b) each independently have one of the definitions specifiedabove.

With regard to suitable and preferred R¹, R², R³, R⁴, R^(a) and R^(b)radicals, reference is made to the above remarks in their entirety.

A further preferred embodiment is that of compounds of the generalformula I.c

whereR¹, R², R³ and R⁴ are each as defined above andX is a divalent bridging group having from 2 to 5 atoms between theflanking bonds,and the structural isomers thereof.

The bridging groups X, together with the N—C═N group to which they arebonded, are preferably a 5- to 8-membered heterocycle which, ifappropriate, is fused singly, doubly or triply to cycloalkyl,heterocycloalkyl, aryl and/or hetaryl, where the fused groups may eachindependently bear one, two, three or four substituents selected fromalkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, thiol, polyalkyleneoxide, polyalkylenimine, COOH, carboxylate, SO₃H, sulfonate, NE¹E²,alkylene-NE¹E², nitro and cyano, where E¹ and E² are each independentlyhydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and/or Xmay have one, two or three substituents which are selected fromoptionally substituted alkyl, optionally substituted cycloalkyl andoptionally substituted aryl, and/or X may be interrupted by 1, 2 or 3optionally substituted heteroatoms.

The bridging groups X are preferably selected from groups of theformulae

in which

-   R^(I), R^(II), R^(III), R^(IV), R^(V) and R^(VI) are each    independently hydrogen, alkyl, alkoxy, cycloalkyl, cycloalkoxy,    heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl,    hetaryloxy, halogen, hydroxyl, thiol, polyalkylene oxide,    polyalkyleneimine, COOH, carboxylate, SO₃H, sulfonate, NE¹E²,    alkylene-NE¹E², nitro, alkoxycarbonyl, acyl or cyano, where E¹ and    E² are each independently hydrogen, alkyl, cycloalkyl,    heterocycloalkyl, aryl or hetaryl.

Some particularly preferred inventive compounds are reproduced below:

It has now been found that, surprisingly, the use of oleum which has aconcentration of more than 20%, and in particular of at least 28%, (forexample, use of 30% oleum) as a solvent in the bromination ofnaphthalenetetracarboxylic bisanhydride surprisingly affords thetetrabromo bisanhydride. It has also been found that this tetrabromobisanhydride can be subjected to

-   -   a full substitution of the bromine atoms by fluorine atoms or        cyano groups,    -   a partial substitution of the bromine atoms by hydrogen, or    -   a partial substitution of the bromine atoms by fluorine atoms or        cyano groups with simultaneous partial substitution by hydrogen.

The invention therefore further provides a process for preparingcompounds of the formula I.a

-   -   in which    -   at least one of the R¹, R², R³ and R⁴ radicals is a substituent        which is selected from Br, F and CN, and the remaining radicals        are each hydrogen,    -   by    -   i) subjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to        a bromination with dibromoisocyanuric acid in the presence of        more than 20% oleum to obtain        2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic        dianhydride

-   -   ii) if appropriate subjecting the        2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic        dianhydride to a substitution of the bromine atoms by fluorine        or by cyano groups, or subjecting the        2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic        dianhydride to a partial substitution of the bromine atoms by        hydrogen and, if appropriate, by fluorine or by cyano groups,    -   iii) if appropriate, subjecting the compounds obtained in        step ii) to at least one separation and/or purification step.        Step i)

For the reaction in step i), preference is given to using at least 25%,in particular at least 28% oleum (for example, 30% oleum).

The molar ratio of dibromoisocyanuric acid tonaphthalene-1,8;4,5-tetracarboxylic bisanhydride is preferably in arange of from about 4:1 to 0.9:1, more preferably from 3:1 to 0.9:1. Themolar ratio is in particular from 4:1 to 1.5:1, especially from 2.5:1 to1.5:1.

Step ii)

Suitable process conditions for the aromatic nucleophilic substitutionof bromine atoms or chlorine atoms by fluorine atoms(halo-dehalogenation) are known in principle. Suitable conditions forhalo-dehalogenation are described, for example, in J. March, AdvancedOrganic Chemistry, 4th edition, John Wiley & Sons publishers (1992), p.659 and also in DE-A-32 35 526. Reference is made here to thisdisclosure.

In a first embodiment, the reaction in step ii) is an exchange of thebromine atoms for fluorine atoms, if appropriate with a partialdehalogenation. To introduce the fluorine groups, preference is given tousing an alkali metal fluoride, in particular KF, NaF or CsF.

Preferred solvents for the halogen exchange in step ii) are aproticpolar solvents such as dimethylformamide, N-methylpyrrolidone, (CH₃)₂SO,dimethyl sulfone or in particular sulfolane. Preference is given tosubjecting the solvents before use to drying to remove water bycustomary methods known to those skilled in the art. This appliesespecially to the removal of residual amounts of water from sulfolane.

For the halogenic exchange in step ii), it is additionally possible touse a complexing agent, for example, a crown ether. These include, forexample, [12]crown-4, [15]crown-5, [18]crown-6, [21]crown-7,[24]crown-8, etc. The complexing agent is selected according to itscapability of complexing the alkali metals of the alkali metal halidesused for the halogen exchange. When KF is used to introduce the fluorinegroups, the complexing agent used is preferably [18]crown-6.

Further suitable phase transfer catalysts for use in step ii) are, forexample, selected from 2-azaallenium compounds, carbophosphazeniumcompounds, aminophosphonium compounds and diphosphazenium compounds. A.Pleschke, A. Marhold, M. Schneider, A. Kolomeitsev and G. V.Roschenthaler give, in Journal of Fluorine Chemistry 125, 2004,1031-1038, a review of further suitable phase transfer catalysts.Reference is made to the disclosure of this document. In a preferredembodiment, 2-azaallenium compounds such as(N,N-dimethylimidazolidino)-tetramethylguanidinium chloride (CNC⁺) areused. Particular preference is then given to using sulfolane as thesolvent. The use amount of the aforementioned phase transfer catalystsis preferably from 0.1 to 20% by weight, more preferably from 1 to 10%by weight, based on the weight of the rylene compound used.

In the case of the reaction with alkali metal fluorides in an anhydrous,aprotic polar solvent, not only a halogen exchange but generally also adehalogenation is effected to a certain degree. The resulting mixturesof dihalo-, trihalo- and/or tetrahalonaphthalenetetracarboxylicanhydrides may subsequently be subjected to a separation.

In a further embodiment, the reaction in step ii) is an exchange of thebromine atoms for cyano groups, if appropriate with a partialdehalogenation. Suitable process conditions for the cyano-dehalogenationare likewise described in J. March, Advanced Organic Chemistry, 4thedition, John Wiley & Sons publishers (1992), pp. 660-661 and also in WO2004/029028. These include, for example, the reaction with coppercyanide. Also suitable are alkali metal cyanides, such as KCN and NaCN,and also zinc cyanide in polar aprotic solvents in the presence ofPd(II) salts or copper or nickel complexes. Preferred polar aproticsolvents are those mentioned above for the halogen exchange.

The separation and/or purification in step iii) may be effected bycustomary methods known to those skilled in the art, such as extraction,distillation, recrystallization, separation on suitable stationaryphases, and a combination of these measures.

It has been found that, surprisingly, halogen- or cyano-substitutednaphthalene-1,8;4,5-tetracarboximides unobtainable to date can beobtained when naphthalene-1,8;4,5-tetracarboxylic dianhydride issubjected first to a bromination, then to substitution of a bromine byfluorine or cyano groups (if appropriate, combined with a partialdehalogenation) and subsequently an imidation. It has also been foundthat halogen- or cyano-substituted naphthalene-1,8;4,5-tetracarboximidesunobtainable to date can be obtained whennaphthalene-1,8;4,5-tetracarboxylic dianhydride is subjected first to animidation, then to a bromination and subsequently, if appropriate, to asubstitution of the bromine by fluorine or cyano groups (if appropriate,combined with a partial dehalogenation). In both process variants, animidation of the bromine-substituted naphthalene-1,8;4,5-tetracarboxylicdianhydride is avoided.

The invention therefore further provides a process for preparingcompounds of the formula

in whichat least one of the R¹, R², R³ and R⁴ radicals is a substituent which isselected from Br, F and CN, and the remaining radicals are eachhydrogen,Z¹, Z², Z³ and Z⁴ are each O,R^(a) and R^(b) are each independently hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl,bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl,orone of the Z¹ or Z² radicals is NR^(c), and R^(a) and R^(c) together area bridging group having 2 to 5 atoms between the flanking bonds, and/orone of the Z³ or Z⁴ radicals is NR^(d), and R^(b) and R^(d) together area bridging group having from 2 to 5 atoms between the flanking bonds, by

-   a1) subjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to a    bromination with N,N′-dibromoisocyanuric acid to obtain a compound    of the general formula I.a

in which two or three or four of the R¹, R², R³ and R⁴ radicals are eachBr, and the remaining radicals are each hydrogen,

-   b1) subjecting the compound of the formula I.a obtained in step a1)    to a substitution of the bromine by fluorine or cyano groups, and    also, if appropriate, partly by hydrogen,-   c1) subjecting the compound obtained in step b1) to a reaction with    an amine of the formula R^(a)—NH₂ and, if appropriate, an amine of    the formula R^(b)—NH₂,    -   or    -   subjecting the compound obtained in step b1) to a reaction with        an amine of the formula H₂N—X—NH₂, where X is a divalent        bridging group having from 2 to 5 atoms between the flanking        bonds.

The invention further provides a process for preparing compounds of theformula

in whichat least one of the R¹, R², R³ and R⁴ radicals is a substituent which isselected from Br, F and CN, and the remaining radicals are eachhydrogen,Z¹, Z², Z³ and Z⁴ are each O,R^(a) and R^(b) are each independently hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl,bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl,orone of the Z¹ or Z² radicals is NR^(c), and R^(a) and R^(c) together area bridging group having 2 to 5 atoms between the flanking bonds, and/orone of the Z³ or Z⁴ radicals is NR^(d), and R^(b) and R^(d) together area bridging group having from 2 to 5 atoms between the flanking bonds, by

-   a2) subjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to a    reaction with an amine of the formula R^(a)—NH₂ and, if appropriate,    an amine of the formula R^(b)—NH₂ to obtain at least one compound of    the general formula I.a21)

where R^(b) may also be as defined for R^(a),orsubjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to a reactionwith an amine of the formula H₂N—X—NH₂ to obtain at least one compoundof the general formula I.a22)

or an isomer thereof, where X is a divalent bridging group having from 2to 5 atoms between the flanking bonds,

-   b2) subjecting the compound(s) obtained in step a2) to a bromination    with N,N′-dibromoisocyanuric acid,-   c2) if appropriate, subjecting the compound(s) obtained in step b2)    to a substitution of the bromine by fluorine or cyano groups, and    also, if appropriate, partly by hydrogen.    Step a1) and step b2)

In a first embodiment, the bromination in steps a1) and b2) is effectedusing oleum which has a concentration of more than 20% (for example byuse of 30% oleum) as a solvent in the bromination to obtain atetrabrominated compound as described above. For the reaction,preference is then given to using at least 25%, in particular at least28% oleum (for example 30% oleum).

In a second embodiment, the bromination is effected in steps a1) and b2)using oleum which has a concentration of at most 20%. In that case,predominantly dibrominated compounds are obtained. The ratio ofdibromoisocyanuric acid to naphthalene-1,8;4,5-tetracarboxylicdianhydride is then preferably within a range from 1.5:1 to 1:1,especially from 1.25:1 to 1:1.

In a preferred embodiment of the second process variant, thenaphthalene-1,8;4,5-tetracarboxylic dianhydride is reacted in step a2)by using amines of the formula R^(a)—NH₂ and, if appropriate, one of theformula R^(b)—NH₂ or amines of the formula H₂N—X—NH₂, where R^(a), R^(b)and X are each groups which cannot be brominated by reaction withdibromocyanuric acid in step b2). The R^(a) and R^(b) radicals are thenpreferably alkyl, cycloalkyl, bicycloalkyl, heterocycloalkyl, aryl orheteroaryl, which may be substituted by radicals which cannot beexchanged for bromine. Since an at least partial bromination of theR^(a), R^(b) and X groups is, however, generally uncritical and maypossibly even be advantageous in the case of use of compounds of theformula I as semiconductors, it is also possible to use brominatablegroups, in which case the amount of dibromocyanuric acid used for thebromination in step b2) has to be increased if appropriate.

Step b1) and step c2)

Suitable process conditions for the aromatic nucleophilic substitutionof bromine atoms by other halogen atoms (halo-dehalogenation), forexample fluorine, or by cyano groups, are those described above in stepii), to which reference is made here.

Step c1) and step a2)

When the imidation in step c1) is effected by subjecting the compoundobtained in step b1) to a reaction with an amine of the formulaR^(a)—NH₂ and, if appropriate, an amine of the formula R^(b)—NH₂, theresult is at least one compound of the general formula I.c1)

in which the R¹, R², R³ and R⁴ radicals, which are each Br in thecompound Ia) obtained in step a), are each F or CN, and some of the R¹,R², R³ and R⁴ radicals, which are each Br in the compound Ia) obtainedin step a), may also be hydrogen,where R^(b) may also be as defined for R^(a) (if only one amine of theformula R^(a)—NH₂ is used for the imidation).

When the imidation in step c1) is effected by subjecting the compoundobtained in step b1) to a reaction with an amine of the formulaH₂N—X—NH₂ where X is a divalent bridging group having from 2 to 5 atomsbetween the flanking bonds, the result is at least one compound of thegeneral formula I.c2)

in which the R¹, R², R³ and R⁴ radicals, which are each Br in thecompound Ia) obtained in step a), are each F or CN, and some of the R¹,R², R³ and R⁴ radicals which are each Br in the compound Ia) obtained instep a), may also be hydrogen.

The imidation of the carboxylic anhydride groups in reaction steps c1)and a2) is known in principle. Preference is given to effecting thereaction of the dianhydride with the primary amine in the presence of apolar aprotic solvent. Suitable polar aprotic solvents are nitrogenheterocycles, such as pyridine, pyrimidine, quinoline, isoquinoline,quinaldine, N-methylpiperidine, N-methylpiperidone andN-methylpyrrolidone.

The reaction may be undertaken in the presence of an imidation catalyst.Suitable imidation catalysts are organic and inorganic acids, forexample formic acid, acetic acid, propionic acid and phosphoric acid.Suitable imidation catalysts are also organic and inorganic salts oftransition metals such as zinc, iron, copper and magnesium. Theseinclude, for example, zinc acetate, zinc propionate, zinc oxide,iron(II) acetate, iron(III) chloride, iron(II) sulfate, copper(II)acetate, copper(II) oxide and magnesium acetate. An imidation catalystis used preferably in the reaction of aromatic amines and is generallyalso advantageous for the reaction of cycloaliphatic amines. In thereaction of aliphatic amines, especially short-chain aliphatic amines,it is generally possible to dispense with the use of an imidationcatalyst. The use amount of the imidation catalyst is preferably from 5to 80% by weight, more preferably from 10 to 75% by weight, based on thetotal weight of the compounds to be amidated.

The molar ratio of amine to dianhydride is preferably from about 2:1 to4:1, more preferably from 2.2:1 to 3:1.

The reaction temperature in steps c1) and a2) is generally from ambienttemperature to 200° C., preferably from 40 to 180° C. The reaction ofaliphatic and cycloaliphatic amines is effected preferably within atemperature range of from about 60° C. to 100° C. The reaction ofaromatic amines is effected preferably within a temperature range offrom about 120 to 160° C.

Preference is given to effecting the reaction in reaction steps c1) anda2) under a protective gas atmosphere, for example nitrogen.

Reaction steps c1) and a2) may be effected at standard pressure or, ifdesired, under elevated pressure. A suitable pressure range is in therange from about 0.8 to 10 bar. When volatile amines are used (boilingpoint about ≦180° C.), preference is given to working under elevatedpressure.

In general, the diimides obtained in reaction steps c1) and a2) may beused for the subsequent reactions without further purification. For useof the products as semiconductors, it may, however, be advantageous tosubject the products to further purification. This includes, forexample, column chromatography processes, where the products arepreferably dissolved in a halogenated hydrocarbon such as methylenechloride, chloroform or tetrachloroethane and are subjected to aseparation or filtration on silica gel. Finally, the solvent is removed.

The inventive compounds and those obtainable by the process according tothe invention are suitable particularly advantageously as organicsemiconductors. They function as n-semiconductors and are notable fortheir air stability. They also possess high charge transport mobilityand have a high on/off ratio. They are suitable particularlyadvantageously for organic field-effect transistors. To preparesemiconductor materials, the inventive compounds may be processedfurther by one of the following processes: printing (offset,flexographic, gravure, screen, inkjet, electrophotography), evaporation,laser transfer, photolithography, drop casting. They are suitable inparticular for use in displays and RFID tags.

The inventive compounds and those obtainable by the process according tothe invention are also suitable particularly advantageously for datastorage, in organic LEDs, in photovoltaics, as UV absorbers, as opticalbrighteners, for optical labels and as fluorescent labels forbiomolecules such as proteins, DNA, sugars and combinations thereof.

The invention is illustrated in detail with reference to thenonrestrictive examples which follow.

EXAMPLES Example 1 2,3,6,7-tetrabromonaphthalene-1,4:5,8-tetracarboxylicdianhydride

A solution of 2.68 g (10 mmol) of naphthalene-1,4:5,8-tetracarboxylicbisanhydride is added dropwise within 4 hours to a solution of 2.86 g(10 mmol) of dibromocyanuric acid in 30% oleum. After the addition hasended, the mixture is stirred at room temperature for another hourbefore it is poured onto 500 ml of ice-water. The precipitate isfiltered off and washed to neutrality with water, washed with methanoland dried under reduced pressure. 3.5 g (60%) of the2,3,6,7-tetrabromonaphthalene-1,4:5,8-tetracarboxylic dianhydride areobtained in the form of a yellowish solid.

Example 2 Mixture of Difluoro- and TetrafluoronaphthalenetetracarboxylicAnhydrides

5 ml of thionyl chloride are added to 32 ml of anhydrous sulfolane, themixture is heated to 130° C. and the volatile constituents are distilledoff. The mixture is cooled to 100° C. Subsequently, 0.85 g (1 mmol) ofthe above-described tetrabromo bisanhydride compound is added thereto,and also 0.1 g of 18-crown-6 and 1.4 g (12 mmol) of dried potassiumfluoride. The mixture is heated at 120° C. and kept at this temperaturefor 2 hours. Subsequently, the mixture is heated to 145° C. and kept atthis temperature for 2 hours. The reaction mixture is cooled to roomtemperature, precipitated in water, filtered and washed with water.According to mass spectroscopy analysis, a mixture of difluoro- andtetrafluoronaphthalic bisanhydride, which comprises a trace oftrifluoronaphthalic bisanhydride, is obtained.

Example 3 2,3,6,7-Tetrabromonaphthalene-1,8;4,5-TetracarboxylicBisanhydride

(further example for the preparation of the compound specified inexample 1)

5.36 g (20 mmol) of 1,8;4,5-naphthalenetetracarboxylic bisanhydride aredissolved in 100 ml of 30% oleum within one hour. At room temperature, asolution of 12.6 g (44 mmol) of dibromoisocyanuric acid in 100 ml of 30%oleum is added to this solution within four hours. After the additionhas ended, the reaction mixture is stirred for 16 hours and then pouredcautiously onto 1000 ml of ice-water, in the course of which a solidprecipitates out. The residue is washed with dilute hydrochloric acidand a little methanol and dried under reduced pressure. 10.8 g (92%) ofa yellow solid are obtained.

Example 4 2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride2,7-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride

At room temperature, a solution of 3.44 g (12 mmol) ofdibromoisocyanuric acid in 100 ml of 20% oleum is added to a solution of2.68 g (10 mmol) of 1,8;4,5-naphthalenetetracarboxylic bisanhydride in50 ml of 20% oleum within four hours. After the addition has ended, themixture is stirred for another hour before the reaction mixture is addedto 2000 ml of ice-water. The mixture is stirred at room temperature for16 hours, filtered and washed with dilute hydrochloric acid and withmethanol, and dried. 3.4 g (80% of a yellow solid with a bromine valueof 36.6% (theoretically 37.5%) are obtained).

According to ¹H NMR in D₂SO₄, the product consists of a 1:1 isomermixture of the two abovementioned compounds.

Example 5 Condensation of ortho-phenylenediamine with2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride2,7-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride

0.21 g (0.5 mmol) of dibromonaphthalenetetracarboxylic bisanhydride isheated to 80° C. in a mixture of 2.5 g of phenol, 0.12 g (1.1 mmol) ofortho-phenylenediamine and 0.09 g (11 mmol) of pyrazine. The reactionmixture is kept at this temperature for 4 hours, then 2.5 ml of methanolare added, and the mixture is cooled to room temperature and filtered.The residue is washed with methanol and dried. 0.19 g (67%) of ablue-black solid is obtained.

Example 6 Condensation of 1,8-diaminonaphthalene with2,6-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride2,7-dibromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride

A mixture of 130 g of phenol, 11.0 g (26 mmol) ofdibromonaphthalenetetracarboxylic bisanhydride, 9.36 g (57 mmol) of1,8-diaminonaphthalene and 4.68 g (57 mmol) of pyrazine is heated to 80°C. for four hours. After cooling to room temperature, 130 ml of methanolare added, and the reaction mixture is stirred for a further 16 hoursand filtered. The blue-black residue is washed with methanol and thenwith warm water and dried in a vacuum drying cabinet.

Example 7 2,3,6,7-Tetracyanonaphthalene-1,8;4,5-tetracarboxylicbisanhydride

A mixture of 0.58 (1 mmol) of2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic dianhydride in 50ml of dioxane is admixed with 1.76 g (15 mmol) of zinc cyanide, 70 mg(0.143 mmol) of 1,1′-bis(diphenylphosphinoferrocene) and 79 mg (143mmol) of tris(dibenzylideneacetone)dipalladium. The mixture is stirredat 100° C. for 22 hours. 5 ml of sulfolane are added and the mixture isstirred at reflux for a further 97 hours. Subsequently, the reactionmixture is diluted with water and the residue which forms is filteredoff, washed with water and dried. 0.46 g of a solid is obtained.

Example 8N,N′-Bis(phenylethyl)-2,6-dibromonaphthalene-1,8;4,5-tetracarboximideN,N′-Bis(phenylethyl)-2,7-dibromonaphthalene-1,8;4,5-tetracarboximide byimidation of 2,3,6,7-tetrabromonaphthalene-1,4;5,8-tetracarboxylicbisanhydride

A mixture of 25 ml of xylene, 2.3 g (4 mmol) of2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride, 1.94g (16 mmol) of phenethylamine is heated to 85° C. for 6 hours and thento 110° C. for one hour. The reaction mixture is cooled to roomtemperature and filtered, and the residue is washed with ethanol. 2.3 gof a solid product are obtained.

Example 9N,N′-Di(2,6-diisopropylphenyl)-2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboximide

Napthalene-1,8;4,5-tetracarboxylic acid (200 mg, 0.343 mmol) and2,6-diisopropylaniline (425 mg, 2.40 mmol) are initially charged inconcentrated acetic acid (5 ml) and stirred at 120° C. for 6 h. This isfollowed by addition of water (50 ml), neutralization with saturatedsodium hydrogencarbonate solution and extraction with chloroform. Thecombined organic phases are dried over sodium sulfate and freed of thesolvent. The residue is eluted with pentane/dichloromethane=2/1 onsilica gel. The target compound is isolated as the second, pale yellowfraction. It can be obtained in pure form by preparative HPLC (RP18)with dichloromethane/methanol=16/84.

Yield: 51 mg (0.051 mmol, 15%)

ESI-MS: calc. for C₅₀H₅₃Br₃N₃O₄ [M+H]⁺: 1000.1558, found: 1000.1478;calc. for C₅₀H₅₂Br₃NaN₃O₄ [M+Na]⁺: 1022.1378, found: 1022.1303.

m.p.: 344.5-346° C.

Example 10 2,3,6,7-Tetrabromonaphthalene-1,8;4,5-tetracarboximide

Naphthalene-1,4,5,8-tetracarboxylic acid (500 mg, 0.857 mmol) andammonium acetate (1.32 g, 17.1 mmol) are heated to reflux withconcentrated acetic acid to initially form a yellow solution. Later, anorange solid precipitates out, which is filtered off while hot after 2h. The substance is washed with concentrated acetic acid (3 ml), water(5 ml), sat. sodium hydrogencarbonate solution (3 ml) and water again (5ml), and then dried over phosphorus pentoxide.

Yield: 150 mg (0.258 mmol, 30%)

EI-MS: calc. for C₁₄H₂Br₄N₂O₄ [M]⁺: 581.7, found: 581.7

m.p. >350° C.

1. A compound of the general formula I

where R¹ and R² are fluorine and R³ and R⁴ are hydrogen, or R¹ and R³are fluorine and R² and R⁴ are hydrogen, or R¹ and R⁴ are fluorine andR² and R³ are hydrogen, Y¹ is NR^(a), where R^(a) is hydrogen orunsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl,cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl orheteroaryl, Y² is NR^(b), where R^(b) is hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl,bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl, Z¹ andZ² are each O and Z³ and Z⁴ are each O.
 2. A process for preparing acompound of the formula (I.a)

in which at least one of the R¹, R², R³ and R⁴ radicals is a substituentwhich is selected from Br, F and CN, and the remaining R¹, R², R³ and R⁴radicals are each hydrogen, comprising: i) subjectingnaphthalene-1,8;4,5-tetracarboxylic dianhydride to a bromination withN,N′-dibromoisocyanuric acid in the presence of more than 20% oleum toobtain 2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic dianhydride

ii) optionally, subjecting the2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic dianhydride to asubstitution of the bromine atoms by fluorine or by cyano groups, orsubjecting the 2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylicdianhydride to a partial substitution of the bromine atoms by hydrogenand, optionally, by fluorine or by cyano groups, and iii) optionally,subjecting the compounds obtained in ii) to at least one separationand/or purification.
 3. The process according to claim 2, wherein analkali metal fluoride is used during the reaction in ii).
 4. The processaccording to claim 2, wherein a copper cyanide or an alkali metalcyanide or zinc cyanide in the presence of Pd(II) salts is used duringthe reaction in ii).
 5. The process according to claim 2, wherein asolvent used in ii) is at least one aprotic polar solvent.
 6. Theprocess according to claim 2, wherein a complexing agent is usedadditionally in ii).
 7. The process according to claim 2, wherein aphase transfer catalyst which is selected from 2-azaallenium compounds,carbophosphazenium compounds, aminophosphonium compounds anddiphosphazenium compounds is additionally used in ii).
 8. A process forpreparing a compound of the following formula

in which at least one of the R¹, R², R³ and R⁴ radicals is a substituentwhich is selected from Br, F and CN, and the remaining R¹, R², R³ and R⁴radicals are each hydrogen, Z¹, Z², Z³ and Z⁴ are each O, R^(a) andR^(b) are each independently hydrogen or unsubstituted or substitutedalkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl,cycloalkenyl, heterocycloalkyl, aryl or heteroaryl, or one of the Z¹ orZ² radicals is NR^(c), and R^(a) and R^(c) together are a bridging grouphaving 2 to 5 atoms between the flanking bonds, and/or one of the Z³ orZ⁴ radicals is NR^(d), and R^(b) and R^(d) together are a bridging grouphaving from 2 to 5 atoms between the flanking bonds, comprising: a1)subjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to abromination with N,N′-dibromoisocyanuric acid to obtain a compound ofthe general formula I.a

 in which two or three or four of the R¹, R², R³ and R⁴ radicals areeach Br, and the remaining R¹, R², R³ and R⁴ radicals are each hydrogen,b1) subjecting the compound of the formula I.a obtained in a1) to asubstitution of the bromine by fluorine or cyano groups, and optionally,partly by hydrogen, and c1) subjecting the compound obtained in b1) to areaction with an amine of the formula R^(a)—NH₂ and, optionally, anamine of the formula R^(b)—NH₂, or  subjecting the compound obtained inb1) to a reaction with an amine of the formula H₂N—X—NH₂, where X is adivalent bridging group having from 2 to 5 atoms between the flankingbonds.
 9. A process for preparing a compound of the following formula

in which at least one of the R¹, R², R³ and R⁴ radicals is a substituentwhich is selected from Br, F and CN, and the R¹, R², R³ and R⁴ remainingradicals are each hydrogen, Z¹, Z², Z³ and Z⁴ are each O, R^(a) andR^(b) are each independently hydrogen or unsubstituted or substitutedalkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl,cycloalkenyl, heterocycloalkyl, aryl or heteroaryl, or one of the Z¹ orZ² radicals is NR^(c), and R^(a) and R^(c) together are a bridging grouphaving 2 to 5 atoms between the flanking bonds, and/or one of the Z³ orZ⁴ radicals is NR^(d), and R^(b) and R^(d) together are a bridging grouphaving from 2 to 5 atoms between the flanking bonds, comprising: a2)subjecting naphthalene-1,8;4,5-tetracarboxylic dianhydride to a reactionwith an amine of the formula R^(a)—NH₂ and, optionally, an amine of theformula R^(b)—NH₂ to obtain at least one compound of the general formulaI.a21)

where R^(b) may also be as defined for R^(a), or subjectingnaphthalene-1,8;4,5-tetracarboxylic dianhydride to a reaction with anamine of the formula H₂N—X—NH₂ to obtain at least one compound of thegeneral formula I.a22)

or an isomer thereof, where X is a divalent bridging group having from 2to 5 atoms between the flanking bonds, b2) subjecting the compound(s)obtained in a2) to a bromination with N,N′-dibromoisocyanuric acid, andc2) optionally, subjecting the compound(s) obtained in b2) to asubstitution of the bromine by fluorine or cyano groups, and also, ifappropriate, partly by hydrogen.
 10. A semiconductor comprising acompound of the general formula I

where at least one of the R¹, R², R³ and R⁴ radicals is a substituentwhich is selected from Br, F and CN, and the remaining R¹, R², R³ and R⁴radicals are each hydrogen, Y¹ is NR^(a), where R^(a) is hydrogen orunsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl,cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl orheteroaryl, Y² is NR^(b), where R^(b) is hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl,bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl, Z¹ andZ² are each O, and Z³ and Z⁴ are each O, wherein one of the followingconditions applies: R¹ and R² are each independently selected fromfluorine and cyano, and R³ and R⁴ are each hydrogen; R¹ and R³ are eachindependently selected from fluorine and cyano, and R² and R⁴ are eachhydrogen; or R¹ and R⁴ are each independently selected from fluorine andcyano, and R² and R³ are each hydrogen.
 11. The process according toclaim 3, wherein the alkali metal fluoride is KF.
 12. The processaccording to claim 5, wherein the solvent is selected from the groupconsisting of dimethylformamide, N-methylpyrrolidone, (CH₃)₂SO, dimethylsulfone, sulfolane, and mixtures thereof.
 13. The process according toclaim 6, wherein the complexing agent is a crown ether.
 14. Thesemiconductor according to claim 10, wherein R¹ and R² are eachindependently selected from fluorine and cyano, and R³ and R⁴ are eachhydrogen.
 15. The semiconductor according to claim 10, wherein R¹ and R³are each independently selected from fluorine and cyano, and R² and R⁴are each hydrogen.
 16. The semiconductor according to claim 10, whereinR¹ and R⁴ are each independently selected from fluorine and cyano, andR² and R³ are each hydrogen.
 17. A semiconductor comprising a compoundof the general formula I

where at least one of the R¹, R², R³ and R⁴ radicals is a substituentwhich is selected from Br, F and CN, and the remaining R¹, R², R³ and R⁴radicals are each hydrogen, Y¹ is NR^(a), where R^(a) is hydrogen or anorganyl radical, Y² is NR^(b), where R^(b) is hydrogen or an organylradical, Z¹ and Z² are each independently O or NR^(c), where R^(c) is anorganyl radical, Z³ and Z⁴ are each independently O or NR^(d), whereR^(d) is an organyl radical, where, in the case that Y¹ is NR^(a) and atleast one of the Z¹ and Z² radicals is NR^(c), R^(a) with one R^(c)radical may also together be a bridging group having 2 to 5 atomsbetween the flanking bonds, and where, in the case that Y² is NR^(b) andat least one of the Z³ and Z⁴ radicals is NR^(d), R^(b) with one R^(d)radical may also together be a bridging group having 2 to 5 atomsbetween the flanking bonds, and provided that one of the following threeconditions apply: R¹ and R² are each independently selected fromfluorine and cyano, and R³ and R⁴ are each hydrogen; or R¹ and R³ areeach independently selected from fluorine and cyano, and R² and R⁴ areeach hydrogen; or R¹ and R⁴ are each independently selected fromfluorine and cyano, and R² and R³ are each hydrogen.
 18. Thesemiconductor according to claim 17, wherein R¹ and R² are eachindependently selected from fluorine and cyano, and R³ and R⁴ are eachhydrogen.
 19. The semiconductor according to claim 17, wherein R¹ and R³are each independently selected from fluorine and cyano, and R² and R⁴are each hydrogen.
 20. The semiconductor according to claim 17, whereinR¹ and R⁴ are each independently selected from fluorine and cyano, andR² and R³ are each hydrogen.